Hβ/Al-SBA-15介微孔复合分子筛负载Ni-W催化剂对萘加氢裂化制BTX的催化性能
|
摘要
采用后合成法制备Hβ/Al-SBA-15复合分子筛,利用XRD、N_2吸附、Py-IR、NH_3-TPD、SEM和TEM等手段进行表征。用浸渍法将Ni-W活性组分担载在Hβ/Al-SBA-15载体上,制备Ni-W/Hβ/Al-SBA-15催化剂,以萘为模型化合物,考察该催化剂的加氢裂化性能。结果表明,所合成的Hβ/Al-SBA-15复合分子筛既有介孔结构又有微孔结构,并同时具有B酸和L酸中心,酸性强于SBA-15。具有适度酸性位和介微孔结构的Ni-W/Hβ/Al-SBA-15催化剂,对萘加氢裂化具有较高的萘转化率和BTX选择性,分别为96%和61.1%。
Micro-mesoporous Hβ/A1-SBA-15 composite molecular sieves was prepared by post-synthesis method and characterized by XRD,N_2 sorption,Py-FTIR,NH_3-TPD,SEM and TEM.With the Hβ/A1-SBA45 composite as support,Ni-W/Hβ/Al-SBA-15 catalyst was prepared through impregnation and its catalytic performance in the hydrocracking of naphthalene to BTX was investigated.The results verified that the Hβ/A1-SBA-15 composite are provided with both micropores and mesopores.Both Bronsted acid and Lewis acid sites are present on the surface of Hβ/A1-SBA-15 and its acidity is stronger than that of SBA-15.After loading Ni and W,the Ni-W/Hβ/Al-SBA-15 catalyst with moderate acidity and micro-mesoporous structure exhibits high activity in the hydrocracking of naphthalene to BTX;the conversion of naphthalene reaches 96%,with the selectivity of 61.1%to BTX.
Micro-mesoporous Hβ/A1-SBA-15 composite molecular sieves was prepared by post-synthesis method and characterized by XRD,N_2 sorption,Py-FTIR,NH_3-TPD,SEM and TEM.With the Hβ/A1-SBA45 composite as support,Ni-W/Hβ/Al-SBA-15 catalyst was prepared through impregnation and its catalytic performance in the hydrocracking of naphthalene to BTX was investigated.The results verified that the Hβ/A1-SBA-15 composite are provided with both micropores and mesopores.Both Bronsted acid and Lewis acid sites are present on the surface of Hβ/A1-SBA-15 and its acidity is stronger than that of SBA-15.After loading Ni and W,the Ni-W/Hβ/Al-SBA-15 catalyst with moderate acidity and micro-mesoporous structure exhibits high activity in the hydrocracking of naphthalene to BTX;the conversion of naphthalene reaches 96%,with the selectivity of 61.1%to BTX.
引文
[1]DONG W L,JAE Y J,TAE W K,SANG E S,SUNG H B.Selective hydro dealkylation of C_9~+aromatics to benzene,toluene and xylenes(BTX)over a Pt/H-ZSM-5 catalyst[J].J Mol Catal A:Chem,2015,407:147-151.
[2]ELFADLY A,ZEID I,YEHIA F,RABIE A,ABOUALALA M,PARK S.Highly selective BTX from catalytic fast pyrolysis of lignin over supported mesoporous silica[J].Int J Biol Macromol,2016,91:278-93.
[3]SULTANA A,FUJITANI T.Conversion of levulinic acid to BTX over different zeolite catalysts[J].Catal Commun,2017,88:26-29.
[4]诸荣,陈航榕,施剑林,严东生.以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征[J].无机材料学报,2003,18(4):855-860.(ZHU Rong,CHEN Hang-rong,SHI Jian-lin,YAN Dong-sheng.Synthesis and characterization of SBA-15 and SBA-16 templated by block copolymers[J].J Inorg Mater,2003,18(4):855-860.)
[5]许峰,顾建峰,关乃佳,袁忠勇.Mg改性ZSM-5/AlPO_4-5复合分子筛用于甲苯甲醇侧链烷基化反应[J].石油学报(石油加工),2008,346(4):346-349.(XU Feng,GU Jian-feng,GUAN Nai-jia,YUAN Zhong-yong.Magnesium modified ZSM-5/AlPO_4-5 composite zeolite for side-chain alkylation of toluene with methanol[J].Acta Pet Sin(Pet Process Sect),2008,346(4):346-349.)
[6]徐新龙,沈健.复合分子筛β/SBA45的合成及表征[J].精细化工,2014,31(5):591-596.(XU Xin-long,SHEN Jian.Synthesis and characterization of composite molecular sieves Beta/SBA-15[J].Fine Chem,2014,31(5):591-596.)
[7]李猛,傅吉全.用ZSM-5降解液进行SBA-15分子筛合成的研究[J].北京化工大学学报(自然科学版),2010,37(4):88-93.(LI Meng,FU Ji-quan.Synthesis of SBA-15 by using the dissolution of ZSM-5 zeolite[J].J Beijing Univ Chem Technol(Nat Sci Ed),2010,37(4):88-93.)
[8]CORMA A.From microporous to mesoporous molecular sieve materials and their use in catalysis[J].Chem Rev,1997,97(6):2373-2419.
[9]王洪平,张泽凯,陈银飞.高硅β分子筛的原位合成及其在甲苯催化燃烧中的应用[J].石油化工,2011,40(11):1158-1164.(WANG Hong-ping,ZHANG Ze-kai,CHEN Yin-fei.In situ synthesis of high-silicaβzeolite over cordierite support and its application in catalytic combustion of toluene[J].Petrkchem Technol,2011,40(11):1158-1164.)
[10]VU X H,URSULA B,MICHAEL H.Direct synthesis of nanosized-ZSM-5/SBA-15 analog composites from preformed ZSM-5 precursors for improved catalytic performance as cracking catalyst[J].J Mater Sci,2014,49(16):5676-5689.
[11]徐新龙,沈健.β/SBA-15复合分子筛的制备及其催化合成叔丁基苯酚的性能[J].石油化工,2014,43(7):767-773.(XU Xin-long,SHEN Jian.Preparation ofβ/SBA-15 composite molecular sieves and their catalytic performances of the synthesis of tert-butyl phenol[J].Petrkchem Technol,2014,43(7):767-773.)
[12]KRESGE C T,LEONOWICZ M E,ROTH W J,VARTULI J C,BECK J S.Ordered mesoporous molecular sieves synthesized by a liquidcrystal template mechanism[J].Nature,1992,359(22):710-712.
[13]CUI Q Y,ZHOU Y S,WEI Q,YU G L ZHU L.Performance of Zr~-and P~-modified USY-based catalyst in hydrocracking of vacuum gas oil[J].Fuel Process Technol,2013,106:439-446.
[14]GANJALA V S P,NEELI C K P,PRAMOD C V.Eco-friendly nitration of benzenes over zeolite-β-SBA-15 composite catalyst[J].Catal Commun,2014,49:82-86.
[15]刘炳四,邱建国,袁兴东.加氢裂化集总动力学模型的研究[J].石油学报(石油加工),1994,10(3):10-18.(LIU Bing-si,QIU Jian-guo,YUAN Xing-dong.Study of lumping kinetic model for hydrocracking[J].Acta Pet Sin(Pet Process Sect),1994,10(3):10-18.)
[2]ELFADLY A,ZEID I,YEHIA F,RABIE A,ABOUALALA M,PARK S.Highly selective BTX from catalytic fast pyrolysis of lignin over supported mesoporous silica[J].Int J Biol Macromol,2016,91:278-93.
[3]SULTANA A,FUJITANI T.Conversion of levulinic acid to BTX over different zeolite catalysts[J].Catal Commun,2017,88:26-29.
[4]诸荣,陈航榕,施剑林,严东生.以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征[J].无机材料学报,2003,18(4):855-860.(ZHU Rong,CHEN Hang-rong,SHI Jian-lin,YAN Dong-sheng.Synthesis and characterization of SBA-15 and SBA-16 templated by block copolymers[J].J Inorg Mater,2003,18(4):855-860.)
[5]许峰,顾建峰,关乃佳,袁忠勇.Mg改性ZSM-5/AlPO_4-5复合分子筛用于甲苯甲醇侧链烷基化反应[J].石油学报(石油加工),2008,346(4):346-349.(XU Feng,GU Jian-feng,GUAN Nai-jia,YUAN Zhong-yong.Magnesium modified ZSM-5/AlPO_4-5 composite zeolite for side-chain alkylation of toluene with methanol[J].Acta Pet Sin(Pet Process Sect),2008,346(4):346-349.)
[6]徐新龙,沈健.复合分子筛β/SBA45的合成及表征[J].精细化工,2014,31(5):591-596.(XU Xin-long,SHEN Jian.Synthesis and characterization of composite molecular sieves Beta/SBA-15[J].Fine Chem,2014,31(5):591-596.)
[7]李猛,傅吉全.用ZSM-5降解液进行SBA-15分子筛合成的研究[J].北京化工大学学报(自然科学版),2010,37(4):88-93.(LI Meng,FU Ji-quan.Synthesis of SBA-15 by using the dissolution of ZSM-5 zeolite[J].J Beijing Univ Chem Technol(Nat Sci Ed),2010,37(4):88-93.)
[8]CORMA A.From microporous to mesoporous molecular sieve materials and their use in catalysis[J].Chem Rev,1997,97(6):2373-2419.
[9]王洪平,张泽凯,陈银飞.高硅β分子筛的原位合成及其在甲苯催化燃烧中的应用[J].石油化工,2011,40(11):1158-1164.(WANG Hong-ping,ZHANG Ze-kai,CHEN Yin-fei.In situ synthesis of high-silicaβzeolite over cordierite support and its application in catalytic combustion of toluene[J].Petrkchem Technol,2011,40(11):1158-1164.)
[10]VU X H,URSULA B,MICHAEL H.Direct synthesis of nanosized-ZSM-5/SBA-15 analog composites from preformed ZSM-5 precursors for improved catalytic performance as cracking catalyst[J].J Mater Sci,2014,49(16):5676-5689.
[11]徐新龙,沈健.β/SBA-15复合分子筛的制备及其催化合成叔丁基苯酚的性能[J].石油化工,2014,43(7):767-773.(XU Xin-long,SHEN Jian.Preparation ofβ/SBA-15 composite molecular sieves and their catalytic performances of the synthesis of tert-butyl phenol[J].Petrkchem Technol,2014,43(7):767-773.)
[12]KRESGE C T,LEONOWICZ M E,ROTH W J,VARTULI J C,BECK J S.Ordered mesoporous molecular sieves synthesized by a liquidcrystal template mechanism[J].Nature,1992,359(22):710-712.
[13]CUI Q Y,ZHOU Y S,WEI Q,YU G L ZHU L.Performance of Zr~-and P~-modified USY-based catalyst in hydrocracking of vacuum gas oil[J].Fuel Process Technol,2013,106:439-446.
[14]GANJALA V S P,NEELI C K P,PRAMOD C V.Eco-friendly nitration of benzenes over zeolite-β-SBA-15 composite catalyst[J].Catal Commun,2014,49:82-86.
[15]刘炳四,邱建国,袁兴东.加氢裂化集总动力学模型的研究[J].石油学报(石油加工),1994,10(3):10-18.(LIU Bing-si,QIU Jian-guo,YUAN Xing-dong.Study of lumping kinetic model for hydrocracking[J].Acta Pet Sin(Pet Process Sect),1994,10(3):10-18.)